Compositions for lipophilic fluid systems comprising 1,2-hexanediol

ABSTRACT

Compositions for treating fabric articles, especially articles of clothing, linens and drapery, wherein the compositions provide improved cleaning of soils from and/or care of and/or treatment of fabric articles, especially while providing superior garment care for articles sensitive to water as compared to conventional fabric article treating compositions, are provided.

RELATED APPLICATIONS

This application is a continuation of U.S. patent application Ser. No.10/177,691, filed on Jun. 21, 2002 now U.S. Pat. No. 6,894,014, whichclaims priority to U.S. Provisional Application Ser. No. 60/300,116filed on Jun. 22, 2001; and a continuation-in-part of U.S. patentapplication Ser. No. 09/849,843, filed on May 4, 2001 now U.S. Pat. No.6,939,837, which claims priority under 35 USC 119(e) to U.S. ProvisionalApplication Ser. No. 60/209,250 filed on Jun. 5, 2000.

FIELD OF THE INVENTION

The present invention relates to compositions for treating fabricarticles, especially articles of clothing, linens and drapery, whereinthe compositions provide improved cleaning of soils from and/or care ofand/or treatment of fabric articles, especially while providing superiorgarment care for articles sensitive to water as compared to conventionalfabric article treating compositions.

BACKGROUND OF THE INVENTION

For the cleaning of fabric articles consumers currently have the choiceof conventional laundry cleaning or dry cleaning.

Conventional laundry cleaning is carried out with relatively largeamounts of water, typically in a washing machine at the consumer's home,or in a dedicated place such as a coin laundry. Although washingmachines and laundry detergents have become quite sophisticated, theconventional laundry process still exposes the fabric articles to a riskof dye transfer and shrinkage. Significant portions of fabric articlesused by consumers are not suitable for cleaning in a conventionallaundry process. Even fabric articles that are considered “washingmachine safe” frequently come out of the laundry process badly wrinkledand require ironing.

Dry cleaning processes rely on non-aqueous solvents for cleaning. Byavoiding water these processes minimize the risk of shrinkage andwrinkling; however, cleaning of soils, particularly water-based andalcohol-based soils, is very limited with these processes. Typically,the dry-cleaner removes such soils by hand prior to the dry-cleaningprocess. These methods are complex, requiring a wide range ofcompositions to address the variety of stains encountered, very laborintensive and often result in some localized damage to the treatedarticle.

Accordingly there is an unmet need, in commercial laundry, indry-cleaning and in the home, for fabric article treating compositions,which simultaneously provide acceptable cleaning of across a variety ofsoils while remaining safe for a wide range of fabric articles.

SUMMARY OF THE INVENTION

The present invention provides compositions which exhibit improvedcleaning of soils from and/or care of and/or treatment of fabricarticles. These benefits may be delivered to the fabric article treatedby the compositions of the present invention while maintaining excellentfabric care properties.

In one aspect of the present invention, a consumable detergentcomposition comprising:

-   -   a) from about 5% to about 60% by weight of the composition of a        siloxane-based surfactant; and    -   b) from about 2% to about 75% by weight of the composition of a        nonionic surfactant; and    -   c) from about 2% to about 40% by weight of the composition of a        polar solvent comprising 1,2-hexanediol.

In another aspect of the present invention, a fabric article treatingcomposition comprising:

-   -   a) from about 70% to about 99.99% by weight of the fabric        article treating composition of decamethylcyclopentasiloxane;    -   b) from about 0.01% to about 10% by weight of the fabric article        treating composition of a siloxane-based surfactant;    -   c) from about 0.01% to about 10% by weight of the fabric article        treating composition of a nonionic surfactant;    -   d) from about 0.001% to about 10% by weight of the fabric        article treating composition of a polar solvent comprising        1,2-hexanediol;    -   e) optionally, from about 0.01% to about 10% by weight of the        fabric article treating composition of other cleaning adjuncts.

In another aspect of the present invention, a consumable detergentcomposition is provided such that upon dilution (i.e., mixing) withdecamethylcyclopentasiloxane, the aforementioned fabric article treatingcompositions are achieved.

In another aspect of the present invention, methods for treating fabricarticles in need of treatment are provided.

In another aspect of the present invention, a method for treating fabricarticles in need of treatment is provided; the method comprises thesteps of:

-   -   a) contacting the fabric articles with        decamethylcyclopentasiloxane in accordance with the present        invention; and    -   b) contacting the fabric articles with a consumable detergent        composition in accordance with the present invention; and    -   c) optionally, subsequently agitating the fabric articles.        Steps a) and b) can occur in any sequence and/or concurrently.

These and other aspects, features and advantages will become apparent tothose of ordinary skill in the art from a reading of the followingdetailed description and the appended claims. All percentages, ratiosand proportions herein are by weight, unless otherwise specified. Alltemperatures are in degrees Celsius (° C) unless otherwise specified.All measurements are in SI units unless otherwise specified. Alldocuments cited are, in relevant part, incorporated herein by reference.

DETAILED DESCRIPTION OF THE INVENTION Definitions

The term “fabric article” used herein is intended to mean any articlethat is customarily cleaned in a conventional laundry process or in adry cleaning process. As such, the term encompasses articles ofclothing, linens, drapery, and clothing accessories. The term alsoencompasses other items made in whole or in part of fabric, such as totebags, furniture covers, tarpaulins and the like.

The term “lipophilic fluid” used herein is intended to mean anynonaqueous fluid capable of removing sebum, as described in more detailherein below.

The term “fabric article treating composition” used herein is intendedto mean any lipophilic fluid-containing composition containing cleaningand/or care additives that come into direct contact with fabric articlesto be cleaned. It should be understood that the term “fabric articletreating composition” encompasses uses other than cleaning, such asconditioning and sizing. Furthermore, optional cleaning adjuncts such asadditional surfactants other than those surfactants described above,bleaches, and the like may be added to the “fabric article treatingcomposition”. That is, cleaning adjuncts may be optionally combined withthe lipophilic fluid. These optional cleaning adjuncts are described inmore detail hereinbelow. Such cleaning adjuncts may be present in thefabric article treating compositions of the present invention at a levelof from about 0.01% to about 10% by weight of the fabric articletreating composition.

The term “soil” means any undesirable substance on a fabric article thatis desired to be removed. By the terms “water-based” or “hydrophilic”soils is meant that the soil comprised water at the time it first camein contact with the fabric article, or the soil retains a significantportion of water on the fabric article. Examples of water-based soilsinclude, but are not limited to, beverages, many food soils, watersoluble dyes, bodily fluids such as sweat, urine or blood, outdoor soilssuch as grass stains and mud.

The term “capable of suspending water in a lipophilic fluid” means thata material is able to suspend, solvate and/or emulsify water, in a waythat the water remains visibly suspended, solvated or emulsified whenleft undisturbed for a period of at least five minutes after initialmixing of the components. In some examples of compositions in accordancewith the present invention, the compositions may be colloidal in natureand/or appear milky. In other examples of compositions in accordancewith the present invention, the compositions may be transparent.

The term “insoluble in a lipophilic fluid” means that when added to alipophilic fluid, a material physically separates from the lipophilicfluid (i.e. settle-out, flocculate, float) within 5 minutes afteraddition, whereas a material that is “soluble in a lipophilic fluid”does not physically separate from the lipophilic fluid within 5 minutesafter addition.

The term “consumable detergent composition” means any detersivecomposition, that when combined with a discrete lipophilic fluid,results in a fabric article treating composition according to thepresent invention.

The term “processing aid” refers to any material that renders theconsumable detergent composition more suitable for formulation,stability, and/or dilution with a lipophilic fluid to form a fabricarticle treating composition in accordance with the present invention.

The term “mixing” as used herein means combining two or more materials(i.e., more specifically a discrete lipophilic fluid and a detergentcomposition in accordance with the present invention) in such a way thata homogeneous mixture or stable dispersion or suspension is formed.Suitable mixing processes are known in the art. Nonlimiting examples ofsuitable mixing processes include vortex mixing processes and staticmixing processes.

Compositions of the Present Invention

The present invention provides compositions which exhibit improvedcleaning of soils (i.e., removal and/or reduction of soils) from and/orcare of and/or treatment of fabric articles. These benefits may bedelivered to the fabric article treated by the compositions of thepresent invention while maintaining excellent fabric care properties,while maintaining excellent fabric care properties.

Lipophilic Fluid

The lipophilic fluid herein is one having a liquid phase present underoperating conditions of a fabric article treating appliance, in otherwords, during treatment of a fabric article in accordance with thepresent invention. In general such a lipophilic fluid can be fullyliquid at ambient temperature and pressure, can be an easily meltedsolid, e.g., one which becomes liquid at temperatures in the range fromabout 0 deg. C. to about 60 deg. C., or can comprise a mixture of liquidand vapor phases at ambient temperatures and pressures, e.g., at 25 deg.C. and 1 atm. pressure. Thus, the lipophilic fluid is not a compressiblegas such as carbon dioxide.

It is preferred that the lipophilic fluids herein be nonflammable orhave relatively high flash points and/or low VOC (volatile organiccompound) characteristics, these terms having their conventionalmeanings as used in the dry cleaning industry, to equal or, preferably,exceed the characteristics of known conventional dry cleaning fluids.

Moreover, suitable lipophilic fluids herein are readily flowable andnon-viscous.

In general, lipophilic fluids herein are required to be fluids capableof at least partially dissolving sebum or body soil as defined in thetest hereinafter. Mixtures of lipophilic fluid are also suitable, andprovided that the requirements of the Lipophilic Fluid Test, asdescribed below, are met, the lipophilic fluid can include any fractionof dry-cleaning solvents, especially newer types including fluorinatedsolvents, or perfluorinated amines. Some perfluorinated amines such asperfluorotributylamines while unsuitable for use as lipophilic fluid maybe present as one of many possible adjuncts present in the lipophilicfluid-containing composition.

Other suitable lipophilic fluids include, but are not limited to,organosilicone solvents including both cyclic and acyclic types, and thelike, and mixtures thereof.

A preferred group of nonaqueous lipophilic fluids suitable forincorporation as a major component of the compositions of the presentinvention include low-volatility nonfluorinated organics, silicones,especially those other than amino functional silicones, and mixturesthereof. Low volatility nonfluorinated organics include for exampleOLEAN® and other polyol esters, or certain relatively nonvolatilebiodegradable mid-chain branched petroleum fractions.

Another preferred group of nonaqueous lipophilic fluids suitable forincorporation as a major component of the compositions of the presentinvention include, but are not limited to, glycol ethers, for examplepropylene glycol methyl ether, propylene glycol n-propyl ether,propylene glycol t-butyl ether, propylene glycol n-butyl ether,dipropylene glycol methyl ether, dipropylene glycol n-propyl ether,dipropylene glycol t-butyl ether, dipropylene glycol n-butyl ether,tripropylene glycol methyl ether, tripropylene glycol n-propyl ether,tripropylene glycol t-butyl ether, tripropylene glycol n-butyl ether.Suitable silicones for use as a major component, e.g., more than 50%, ofthe composition include cyclopentasiloxanes, sometimes termed “D5”,and/or linear analogs having approximately similar volatility,optionally complemented by other compatible silicones. Suitablesilicones are well known in the literature, see, for example, KirkOthmer's Encyclopedia of Chemical Technology, and are available from anumber of commercial sources, including General Electric, ToshibaSilicone, Bayer, and Dow Corning. Other suitable lipophilic fluids arecommercially available from Procter & Gamble or from Dow Chemical andother suppliers.

Qualification of Lipophilic Fluid and Lipophilic Fluid Test (LF Test)

Any nonaqueous fluid that is both capable of meeting known requirementsfor a dry-cleaning fluid (e.g, flash point etc.) and is capable of atleast partially dissolving sebum, as indicated by the test methoddescribed below, is suitable as a lipophilic fluid herein. As a generalguideline, perfluorobutylamine (Fluorinert FC-43®) on its own (with orwithout adjuncts) is a reference material which by definition isunsuitable as a lipophilic fluid for use herein (it is essentially anonsolvent) while cyclopentasiloxanes have suitable sebum-dissolvingproperties and dissolves sebum.

The following is the method for investigating and qualifying othermaterials, e.g., other low-viscosity, free-flowing silicones, for use asthe lipophilic fluid. The method uses commercially available Crisco®canola oil, oleic acid (95% pure, available from Sigma Aldrich Co.) andsqualene (99% pure, available from J.T. Baker) as model soils for sebum.The test materials should be substantially anhydrous and free from anyadded adjuncts, or other materials during evaluation.

Prepare three vials, each vial will contain one type of lipophilic soil.Place 1.0 g of canola oil in the first; in a second vial place 1.0 g ofthe oleic acid (95%), and in a third and final vial place 1.0 g of thesqualene (99.9%). To each vial add 1 g of the fluid to be tested forlipophilicity. Separately mix at room temperature and pressure each vialcontaining the lipophilic soil and the fluid to be tested for 20 secondson a standard vortex mixer at maximum setting. Place vials on the benchand allow to settle for 15 minutes at room temperature and pressure. If,upon standing, a clear single phase is formed in any of the vialscontaining lipophilic soils, then the nonaqueous fluid qualifies assuitable for use as a “lipophilic fluid” in accordance with the presentinvention. However, if two or more separate layers are formed in allthree vials, then the amount of nonaqueous fluid dissolved in the oilphase will need to be further determined before rejecting or acceptingthe nonaqueous fluid as qualified.

In such a case, with a syringe, carefully extract a 200-microlitersample from each layer in each vial. The syringe-extracted layer samplesare placed in GC auto sampler vials and subjected to conventional GCanalysis after determining the retention time of calibration samples ofeach of the three models soils and the fluid being tested. If more than1% of the test fluid by GC, preferably greater, is found to be presentin any one of the layers which consists of the oleic acid, canola oil orsqualene layer, then the test fluid is also qualified for use as alipophilic fluid. If needed, the method can be further calibrated usingheptacosafluorotributylamine, i.e., Fluorinert FC-43 (fail) andcyclopentasiloxane (pass). A suitable GC is a Hewlett Packard GasChromatograph HP5890 Series II equipped with a split/splitless injectorand FID. A suitable column used in determining the amount of lipophilicfluid present is a J&W Scientific capillary column DB-1HT, 30 meter,0.25 mm id, 0.1 um film thickness cat# 1221131. The GC is suitablyoperated under the following conditions:

Carrier Gas: Hydrogen

Column Head Pressure: 9 psi

Flows: Column Flow @ ˜1.5 ml/min.

-   -   Split Vent @ ˜250–500 ml/min.    -   Septum Purge @ 1 ml/min.

Injection: HP 7673 Autosampler, 10 ul syringe, 1 ul injection

Injector Temperature: 350° C.

Detector Temperature: 380° C.

Oven Temperature Program: initial 60° C. hold 1 min.

-   -   rate 25° C./min.    -   final 380° C. hold 30 min.

Preferred lipophilic fluids suitable for use herein can further bequalified for use on the basis of having an excellent garment careprofile. Garment care profile testing is well known in the art andinvolves testing a fluid to be qualified using a wide range of garmentor fabric article components, including fabrics, threads and elasticsused in seams, etc., and a range of buttons. Preferred lipophilic fluidsfor use herein have an excellent garment care profile, for example theyhave a good shrinkage and/or fabric puckering profile and do notappreciably damage plastic buttons. Certain materials which in sebumremoval qualify for use as lipophilic fluids, for example ethyl lactate,can be quite objectionable in their tendency to dissolve buttons, and ifsuch a material is to be used in the compositions of the presentinvention, it will be formulated with water and/or other solvents suchthat the overall mix is not substantially damaging to buttons. Otherlipophilic fluids, D5, for example, meet the garment care requirementsquite admirably. Some suitable lipophilic fluids may be found in grantedU.S. Pat. Nos. 5,865,852; 5,942,007; 6,042,617; 6,042,618; 6,056,789;6,059,845; and 6,063,135, which are incorporated herein by reference.

Lipophilic fluids can include linear and cyclic polysiloxanes,hydrocarbons and chlorinated hydrocarbons, with the exception of PERCwhich is explicitly not covered by the lipophilic fluid definition asused herein. (Specifically call out DF2000 and PERC). More preferred arethe linear and cyclic polysiloxanes and hydrocarbons of the glycolether, acetate ester, lactate ester families. Preferred lipophilicfluids include cyclic siloxanes having a boiling point at 760 mm Hg. ofbelow about 250° C. Specifically preferred cyclic siloxanes for use inthis invention are octamethylcyclotetrasiloxane,decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane.Preferably, the cyclic siloxane comprises decamethylcyclopentasiloxane(D5, pentamer) and is substantially free of octamethylcyclotetrasiloxane(tetramer) and dodecamethylcyclohexasiloxane (hexamer).

However, it should be understood that useful cyclic siloxane mixturesmight contain, in addition to the preferred cyclic siloxanes, minoramounts of other cyclic siloxanes including octamethylcyclotetrasiloxaneand hexamethylcyclotrisiloxane or higher cyclics such astetradecamethylcycloheptasiloxane. Generally the amount of these othercyclic siloxanes in useful cyclic siloxane mixtures will be less thanabout 10 percent based on the total weight of the mixture. The industrystandard for cyclic siloxane mixtures is that such mixtures compriseless than about 1% by weight of the mixture ofoctamethylcyclotetrasiloxane.

Accordingly, the lipophilic fluid of the present invention preferablycomprises more than about 50%, more preferably more than about 75%, evenmore preferably at least about 90%, most preferably at least about 95%by weight of the lipophilic fluid of decamethylcyclopentasiloxane.Alternatively, the lipophilic fluid may comprise siloxanes which are amixture of cyclic siloxanes having more than about 50%, preferably morethan about 75%, more preferably at least about 90%, most preferably atleast about 95% up to about 100% by weight of the mixture ofdecamethylcyclopentasiloxane and less than about 10%, preferably lessthan about 5%, more preferably less than about 2%, even more preferablyless than about 1%, most preferably less than about 0.5% to about 0% byweight of the mixture of octamethylcyclotetrasiloxane and/ordodecamethylcyclohexasiloxane.

The level of lipophilic fluid, when present in the fabric articletreating compositions according to the present invention, is preferablyfrom about 70% to about 99.99%, more preferably from about 90% to about99.9%, and even more preferably from about 95% to about 99.8% by weightof the fabric article treating composition.

The level of lipophilic fluid, when present in the consumable detergentcompositions according to the present invention, is preferably fromabout 0.1% to about 90%, more preferably from about 0.5% to about 75%,and even more preferably from about 1% to about 50% by weight of theconsumable detergent composition.

Surfactant Component

The surfactant component of the present invention can be a material thatis capable of suspending water in a lipophilic fluid and/or enhancingsoil removal benefits of a lipophilic fluid. The materials may besoluble in the lipophilic fluid.

One class of materials can include siloxane-based surfactants(siloxane-based materials). The siloxane-based surfactants in thisapplication may be siloxane polymers for other applications. Thesiloxane-based surfactants typically have a weight average molecularweight from 500 to 20,000. Such materials, derived frompoly(dimethylsiloxane), are well known in the art. In the presentinvention, not all such siloxane-based surfactants are suitable, becausethey do not provide improved cleaning of soils compared to the level ofcleaning provided by the lipophilic fluid itself.

Suitable siloxane-based surfactants comprise a polyether siloxane havingthe formula:M_(a)D_(b)D′_(c)D″_(d)M′_(2-a)wherein a is 0–2; b is 0–1000; c is 0–50; d is 0–50, provided that a+c+dis at least 1;

M is R¹ _(3-e)X_(e)SiO_(½) wherein R¹ is independently H, or amonovalent hydrocarbon group, X is hydroxyl group, and e is 0 or 1;

M′ is R² ₃SiO_(½) wherein R² is independently H, a monovalenthydrocarbon group, or(CH₂)_(f)—(C6H4)_(g)O—(C₂H₄O)_(h)—(C₃H₆O)_(i)—(C_(k)H_(2k)O)_(j)—R₃,provided that at least one R² is(CH₂)_(f)—(C6H4)_(g)O—(C₂H₄O)_(h)—(C₃H₆O)_(i)—(C_(k)H_(2k)O)_(j)—R₃,wherein R³ is independently H, a monovalent hydrocarbon group or analkoxy group, f is 1–10, g is 0 or 1, h is 1–50, i is 0–50, j is 0–50, kis 4–8;

D is R⁴ ₂SiO_(2/2) wherein R⁴ is independently H or a monovalenthydrocarbon group;

D′ is R⁵ ₂SiO_(2/2) wherein R⁵ is independently R² provided that atleast one R⁵ is (CH₂)_(f)—(C6H4)_(g)O—(C₂H₄O)_(h)—(C₃H₆O)_(i)—(C_(k)H_(2k)O)_(j)—R₃, wherein R³ isindependently H, a monovalent hydrocarbon group or an alkoxy group, f is1–10, g is 0 or 1, h is 1–50, i is 0–50, j is 0–50, k is 4–8; and

D″ is R⁶ ₂SiO_(2/2) wherein R⁶ is independently H, a monovalenthydrocarbon group or(CH₂)_(l)(C₆H₄)_(m)(A)_(n)-[(L)_(o)—(A′)_(p)−]_(q)−(L′)_(r)Z(G)_(s),wherein 1 is 1–10; m is 0 or 1; n is 0–5; o is 0–3; p is 0 or 1; q is0–10; r is 0–3; s is 0–3; C₆H₄ is unsubstituted or substituted with aC₁₋₁₀ alkyl or alkenyl; A and A′ are each independently a linking moietyrepresenting an ester, a keto, an ether, a thio, an amido, an amino, aC₁₋₄ fluoroalkyl, a C₁₋₄ fluoroalkenyl, a branched or straight chainedpolyalkylene oxide, a phosphate, a sulfonyl, a sulfate, an ammonium, andmixtures thereof; L and L′ are each independently a C₁₋₃₀ straightchained or branched alkyl or alkenyl or an aryl which is unsubstitutedor substituted; Z is a hydrogen, carboxylic acid, a hydroxy, aphosphato, a phosphate ester, a sulfonyl, a sulfonate, a sulfate, abranched or straight-chained polyalkylene oxide, a nitryl, a glyceryl,an aryl unsubstituted or substituted with a C₁₋₃₀ alkyl or alkenyl, acarbohydrate unsubstituted or substituted with a C₁₋₁₀ alkyl or alkenylor an ammonium; G is an anion or cation such as H⁺, Na⁺, Li⁺, K⁺, NH₄ ⁺,Ca⁺², Mg⁺², Cl⁻, Br⁻, I⁻, mesylate or tosylate.

Examples of the types of siloxane-based surfactants described hereinabove may be found in EP-1,043,443A1, EP-1,041,189 and WO-01/34,706 (allto GE Silicones) and U.S. Pat. No. 5,676,705, U.S. Pat. No. 5,683,977,U.S. Pat. No. 5,683,473, and EP-1,092,803A1 (all to Lever Brothers).

Nonlimiting commercially available examples of suitable siloxane-basedsurfactants are TSF 4446 (ex. General Electric Silicones), XS69-B5476(ex. General Electric Silicones); Jenamine HSX (ex. DelCon) and Y12147(ex. OSi Specialties).

A second preferred class of materials suitable for the surfactantcomponent is organic in nature. Preferred materials areorganosulfosuccinate surfactants, with carbon chains of from about 6 toabout 20 carbon atoms. Most preferred are organosulfosuccinatescontaining dialkly chains, each with carbon chains of from about 6 toabout 20 carbon atoms. Also preferred are chains containing aryl oralkyl aryl, substituted or unsubstituted, branched or linear, saturatedor unsaturated groups.

Nonlimiting commercially available examples of suitableorganosulfosuccinate surfactants are available under the trade names ofAerosol® OT and Aerosol® TR-70 (ex. Cytec).

The surfactant component, when present in the fabric article treatingcompositions of the present invention, preferably comprises from about0.01% to about 10%, more preferably from about 0.02% to about 5%, evenmore preferably from about 0.05% to about 2% by weight of the fabricarticle treating composition.

The surfactant component, when present in the consumable detergentcompositions of the present invention, preferably comprises from about1% to about 99%, more preferably 2% to about 75%, even more preferablyfrom about 5% to about 60% by weight of the consumable detergentcomposition.

Non-Silicone Additive

The non-silicone additive (i.e., materials do not contain an Si atom),which preferably comprises a strongly polar and/or hydrogen-bonding headgroup, further enhances soil removal by the compositions of the presentinvention. Examples of the strongly polar and/or hydrogen-bonding headgroup-containing materials include, but are not limited to alcohols,cationic materials such as cationic surfactants, quaternary surfactants,quaternary ammonium salts such as ammonium chlorides (nonlimitingexamples of ammonium chlorides are Arquad materials commerciallyavailable from Akzo Nobel) and cationic fabric softening actives,nonionic materials such as nonionic surfactants (i.e., alcoholethoxylates, polyhydroxy fatty acid amides), gemini surfactants, anionicsurfactants, zwitterionic surfactants, carboxylic acids, sulfates,sulphonates, phosphates, phosphonates, and nitrogen containingmaterials. In one embodiment, non-silicone additives comprise nitrogencontaining materials selected from the group consisting of primary,secondary and tertiary amines, diamines, triamines, ethoxylated amines,amine oxides, amides and betaines, a nonlimiting example of a betainesis Schercotaine materials commercially available from Scher Chemicalsand mixtures thereof.

In another embodiment embodiment, alkyl chain contains branching thatmay help lower the melting point.

In yet another embodiment, primary alkylamines comprising from about 6to about 22 carbon atoms are used. Particularly preferred primaryalkylamines are oleylamine (commercially available from Akzo under thetrade name Armeen® OLD), dodecylamine (commercially available from Akzounder the trade name Armeen® 12D), branched C₁₆–C₂₂ alkylamine(commercially available from Rohm & Haas under the trade name Primene®JM-T) and mixtures thereof.

Suitable cationic materials may include quaternary surfactants, whichmaybe quaternary ammonium compounds. Commercially available agentsinclude Varisoft materials from Goldschmidt.

Additional suitable cationic materials may include conventional fabricsoftening actives. Nonlimiting examples of suitable fabric softeningactives of the invention comprise a majority of compounds as follows:

Diester Quaternary Ammonium Fabric Softening Active Compound (DEQA)

(1) The first type of DEQA preferably comprises, as the principalactive, compounds of the formula{R_(4-m)—N⁺—[(CH₂)_(n)—Y—R¹]_(m)}A⁻wherein each R substituent is either hydrogen, a short chain C₁–C₆,preferably C₁–C₃ alkyl or hydroxyalkyl group, e.g., methyl (mostpreferred), ethyl, propyl, hydroxyethyl, and the like, poly (C₂₋₃alkoxy)preferably polyethoxy group, benzyl, or mixtures thereof; each m is 2 or3; each n is from 1 to about 4; each Y is —O—(O)C—, —C(O)—O—, —NR—C(O)—,or —C(O)—NR—; the sum of carbons in each R¹, plus one when Y is —O—(O)C—or —NR—C(O)—, is C₁₂–C₂₂, preferably C₁₄–C₂₀, with each R¹ being ahydrocarbyl, or substituted hydrocarbyl group, and A⁻ can be anysoftener-compatible anion, preferably, chloride, bromide, methylsulfate,ethylsulfate, sulfate, and nitrate, more preferably chloride or methylsulfate. (As used herein, the “percent of softening active” containing agiven R¹ group is based upon taking a percentage of the total activebased upon the percentage that the given R¹ group is, of the total R¹groups present.)

(2) A second type of DEQA active has the general formula:[R₃N⁺CH₂CH(YR¹)(CH₂YR¹)]A⁻wherein each Y, R, R¹, and A⁻ have the same meanings as before. Suchcompounds include those having the formula:[CH₃]₃ N⁽⁺⁾[CH₂CH(CH₂O(O)CR¹)O(O)CR¹]Cl⁽⁻⁾where each R is a methyl or ethyl group and preferably each R¹ is in therange of C₁₅ to C₁₉.

(3) The DEQA actives described hereinabove also include the neutralizedamine softening actives wherein at least one R group is a hydrogen atom.A non-limiting example of actives of this type is the chloride salt of(unsaturated alkoyloxyethyl)(unsaturatedalkylamidotrimethylene)methylamine. Other examples of suitable aminesoftening actives are disclosed in PCT application WO 99/06509, K. A.Grimm, D. R. Bacon, T. Trinh, E. H. Wahl, and H. B. Tordil, published onFeb. 11, 1999, said application being incorporated herein by reference.

(4) Polyquaternary Ammonium Softening Actives. Fabric softening activescarrying more than one positive quaternary ammonium charge are alsouseful in the rinse-added compositions of the present invention. Anexample of this type of softening active is that having the formula:

wherein each R is H or a short chain C₁–C₆, preferably C₁–C₃ alkyl orhydroxyalkyl group, e.g., methyl (most preferred), ethyl, propyl,hydroxyethyl, and the like, benzyl, or (R²O)₂₋₄H; each R¹ is a C₆–C₂₂,preferably C₁₄–C₂₀ hydrocarbyl, or substituted hydrocarbyl substituent,preferably C₁₀–C₂₀ alkyl or alkenyl (unsaturated alkyl, includingpolyunsaturated alkyl, also referred to sometimes as “alkylene”), mostpreferably C₁₂–C₁₈ alkyl or alkenyl; each R² is a C₁₋₆ alkylene group,preferably an ethylene group; and A⁻ are defined as below. Fabricsoftening actives having the following formula:

wherein R¹ is derived from oleic acid is available from Witco Company.

(5) Softening active having the formula:R_(4-m)—N⁽⁺⁾—R¹ _(m)A⁻wherein each m is 2 or 3, each R¹ is a C₆–C₂₂, preferably C₁₄–C₂₀, butno more than one being less than about C₁₂ and then the other is atleast about 16, hydrocarbyl, or substituted hydrocarbyl substituent,preferably C₁₀–C₂₀ alkyl or alkenyl, most preferably C₁₂–C₁₈ alkyl oralkenyl, and where the Iodine Value of a fatty acid containing this R¹group is from 0 to about 140, more preferably from about 40 to about130; with a cis/trans ratio of from about 1:1 to about 50:1, the minimumbeing 1:1, preferably from about 2:1 to about 40:1, more preferably fromabout 3:1 to about 30:1, and even more preferably from about 4:1 toabout 20:1; each R¹ can also be a branched chain C₁₄–C₂₂ alkyl group,preferably a branched chain C₁₆–C₁₈ group; each R is H or a short chainC₁–C₆, preferably C₁–C₃ alkyl or hydroxyalkyl group, e.g., methyl (mostpreferred), ethyl, propyl, hydroxyethyl, and the like, benzyl, or(R²O)₂₋₄H; and A⁻ is a softening active compatible anion, preferably,chloride, bromide, methylsulfate, ethylsulfate, sulfate, and nitrate,more preferably chloride and methyl sulfate;

(6) Softening active having the formula:

wherein each R, R¹, and A⁻ have the definitions given above; each R² isa C₁₋₆ alkylene group, preferably an ethylene group; and G is an oxygenatom or an —NR— group;

(7) Softening active having the formula:

wherein R¹, R² and G are defined as above in (6);

(8) Reaction products of substantially unsaturated and/or branched chainhigher fatty acids with dialkylenetriamines in, e.g., a molecular ratioof about 2:1, said reaction products containing compounds of theformula:R¹—C(O)—NH—R²—NH—R³—NH—C(O)—R¹wherein R¹, R² are defined as above in (6), and each R³ is a C₁₋₆alkylene group, preferably an ethylene group;

(9) Softening active having the formula:[R¹—C(O)—NR—R²—N(R)₂—R³—NR—C(O)—R¹]⁺A⁻wherein R, R¹, R², R³ and A⁻ are defined as above in (6) and (8);

(10) The reaction product of substantially unsaturated and/or branchedchain higher fatty acid with hydroxyalkylalkylenediamines in a molecularratio of about 2:1, said reaction products containing compounds of theformula:R¹—C(O)—NH—R²—N(R³OH)—C(O)—R¹wherein R¹, R² and R³ are defined as above in (8); and

(11) Mixtures thereof.

Examples of Compound (5) are dialkylenedimethylammonium salts such asdicanoladimethylammonium chloride, dicanoladimethylammoniummethylsulfate, di(partially hydrogenated soybean, cis/trans ratio ofabout 4:1)dimethylammonium chloride, dioleyldimethylammonium chloride.Dioleyldimethylammonium chloride and di(canola)dimethylammonium chlorideare preferred. An example of commercially availabledialkylenedimethylammonium salts usable in the present invention isdioleyldimethylammonium chloride available from Witco Corporation underthe trade name Adogen® 472.

An example of Compound (6) is1-methyl-1-oleylamidoethyl-2-oleylimidazolinium methylsulfate wherein R¹is an acyclic aliphatic C₁₅–C₁₇ hydrocarbon group, R² is an ethylenegroup, G is a NH group, R⁵ is a methyl group and A⁻ is a methyl sulfateanion, available commercially from the Witco Corporation under the tradename Varisoft® 3690.

An example of Compound (7) is 1-oleylamidoethyl-2-oleylimidazolinewherein R¹ is an acyclic aliphatic C₁₅–C₁₇ hydrocarbon group, R² is anethylene group, and G is a NH group.

An example of Compound (8) is reaction products of oleic acids withdiethylenetriamine in a molecular ratio of about 2:1, said reactionproduct mixture containing N,N″-dioleoyldiethylenetriamine with theformula:R¹—C(O)—NH—CH₂CH₂—NH—CH₂CH₂—NH—C(O)—R¹wherein R¹—C(O) is oleoyl group of a commercially available oleic acidderived from a vegetable or animal source, such as Emersol® 223LL orEmersol® 7021, available from Henkel Corporation, and R² and R³ aredivalent ethylene groups.

An example of Compound (9) is a difatty amidoamine based softeningactive having the formula:[R¹—C(O)—NH—CH₂CH₂—N(CH₃)(CH₂CH₂OH)—CH₂CH₂—NH—C(O)—R¹]⁺CH₃SO₄ ⁻wherein R¹—C(O) is oleoyl group, available commercially from the WitcoCorporation under the trade name Varisoft® 222LT.

An example of Compound (10) is reaction products of oleic acids withN-2-hydroxyethylethylenediamine in a molecular ratio of about 2:1, saidreaction product mixture containing a compound of the formula:R¹—C(O)—NH—CH₂CH₂—N(CH₂CH₂OH)—C(O)—R¹wherein R¹—C(O) is oleoyl group of a commercially available oleic acidderived from a vegetable or animal source, such as Emersol® 223LL orEmersol® 7021, available from Henkel Corporation.

The above individual Compounds (actives) can be used individually or asmixtures.

One type of optional but highly desirable cationic compound which can beused in combination with the above softening actives are compoundscontaining one long chain acyclic C₈–C₂₂ hydrocarbon group, selectedfrom the group consisting of: wherein R⁷ is hydrogen or a C₁–C₄saturated alkyl or hydroxyalkyl group, and R¹ and A⁻ are defined asherein above;

(12) Acyclic quaternary ammonium salts having the formula:[R¹—N(R⁵)₂—R⁶]⁺A⁻wherein R⁵ and R⁶ are C₁–C₄ alkyl or hydroxyalkyl groups, and R¹ and A⁻are defined as hereinabove in (9);

(13) Substituted imidazolinium salts having the formula:

wherein R⁷ is hydrogen or a C₁–C₄ saturated alkyl or hydroxyalkyl group,and R¹ and A⁻ are defined as hereinabove in (9);

(14) Substituted imidazolinium salts having the formula:

wherein R⁵ is a C₁–C₄ alkyl or hydroxyalkyl group, and R¹, R², and A⁻are as defined above in (9);

(15) Alkylpyridinium salts having the formula:

wherein R⁴ is an acyclic aliphatic C₈–C₂₂ hydrocarbon group and A⁻ is ananion;

(16) Alkanamide alkylene pyridinium salts having the formula:

wherein R¹, R² and A⁻ are defined as herein above; and

(17) Monoalkyl diquaternary salts, e.g., that having the formula:A⁻[R¹—N⁽⁺⁾(R)₂—R²N⁽⁺⁾(R)₃]A⁻wherein R, R¹, R² and A⁻ are defined as herein above in (6) and (9); and

(18) Mixtures thereof.

Examples of Compound (12) are the monoalkenyltrimethylammonium saltssuch as monooleyltrimethylammonium chloride, monocanolatrimethylammoniumchloride, and soyatrimethylammonium chloride. Monooleyltrimethylammoniumchloride and monocanolatrimethylammonium chloride are preferred. Otherexamples of Compound (12) are soyatrimethylammonium chloride availablefrom Witco Corporation under the trade name Adogen® 415,erucyltrimethylammonium chloride wherein R¹ is a C₂₂ hydrocarbon groupderived from a natural source; soyadimethylethylammonium ethylsulfatewherein R¹ is a C₁₆–C₁₈ hydrocarbon group, R⁵ is a methyl group, R⁶ isan ethyl group, and A⁻ is an ethylsulfate anion; and methylbis(2-hydroxyethyl)oleylammonium chloride wherein R¹ is a C₁₈hydrocarbon group, R⁵ is a 2-hydroxyethyl group and R⁶ is a methylgroup.

An example of Compound (14) is1-ethyl-1-(2-hydroxyethyl)-2-isoheptadecylimidazolinium ethylsulfatewherein R¹ is a C₁₇ hydrocarbon group, R² is an ethylene group, R⁵ is anethyl group, and A⁻ is an ethylsulfate anion.

An example of Compound (17) is N-tallow pentamethyl propane diammoniumdichloride, with the formula:Cl⁻[(tallowalkyl)—N⁽⁺⁾(CH₃)₂—CH₂—CH₂—N⁽⁺⁾(CH₃)₃]Cl⁻available from Witco Corporation under the trade name Adogen® 477.

In the cationic nitrogenous salts herein, the anion A⁻, which is anysoftening active compatible anion, provides electrical neutrality. Mostoften, the anion used to provide electrical neutrality in these salts isfrom a strong acid, especially a halide, such as chloride,methylsulfate, bromide, or iodide. However, other anions can be used,such as ethylsulfate, acetate, formate, sulfate, carbonate, and thelike. Chloride and methylsulfate are preferred herein as anion A.

Suitable cationic surfactants include, but are not limited todialkyldimethylammonium salts having the formula:R′R″N⁺(CH₃)₂X⁻wherein each R′ and R″ is independently selected from the groupconsisting of 12–30 C atoms or derived from tallow, coconut oil or soy,X═Cl or Br, Nonlimiting examples include: didodecyldimethylammoniumbromide (DDAB), dihexadecyldimethyl ammonium chloride,dihexadecyldimethyl ammonium bromide, dioctadecyldimethyl ammoniumchloride, dieicosyldimethyl ammonium chloride, didocosyldimethylammonium chloride, dicoconutdimethyl ammonium chloride, ditallowdimethylammonium bromide (DTAB). Commercially available examples include, butare not limited to: ADOGEN, ARQUAD, TOMAH, VARIQUAT.

In one embodiment, the cationic surfactants comprise the water-solublequaternary ammonium compounds useful in the present composition havingthe formula:R₁R₂R₃R₄N⁺X⁻wherein R₁ is C₈–C₁₆ alkyl, each of R₂, R₃ and R₄ is independently C₁–C₄alkyl, C₁–C₄ hydroxy alkyl, benzyl, and —(C₂H₄₀)_(x)H where x has avalue from 2 to 5, and X is an anion. Not more than one of R₂, R₃ or R₄should be benzyl.

The typical cationic fabric softening compounds include thewater-insoluble quaternary-ammonium fabric softening actives, the mostcommonly used having been di(long alkylchain)dimethylammonium (C₁–C₄alkyl)sulfate or chloride, preferably the methyl sulfate, compoundsincluding the following:

-   1) di(tallowalkyl)dimethylammonium methyl sulfate (DTDMAMS);-   2) di(hydrogenated tallowalkyl)dimethylammonium methyl sulfate;-   3) di(hydrogenated tallowalkyl)dimethylammonium chloride (DTDMAC);-   4) distearyldimethylammonium methyl sulfate;-   5) dioleyldimethylammonium methyl sulfate;-   6) dipalmitylhydroxyethylmethylammonium methyl sulfate;-   7) stearylbenzyldimethylammonium methyl sulfate;-   8) tallowalkyltrimethylammonium methyl sulfate;-   9) (hydrogenated tallowalkyl)trimethylammonium methyl sulfate;-   10) (C₁₂₋₁₄ alkyl)hydroxyethyldimethylammonium methyl sulfate;-   11) (C₁₂₋₁₈ alkyl)di(hydroxyethyl)methylammonium methyl sulfate;-   12) di(stearoyloxyethyl)dimethylammonium chloride;-   13) di(tallowoyloxyethyl)dimethylammonium methyl sulfate;-   14) ditallowalkylimidazolinium methyl sulfate;-   15) 1-(2-tallowylamidoethyl)-2-tallowylimidazolinium methyl sulfate;    and-   16) mixtures thereof.

Suitable nonionic surfactants include, but are not limited to:

-   -   a) Polyethylene oxide condensates of nonyl phenol and myristyl        alcohol, such as in U.S. Pat. No. 4,685,930 Kasprzak; and    -   b) fatty alcohol ethoxylates, R—(OCH₂CH₂)_(a)OH a=1 to 100,        typically 12–40, R=hydrocarbon residue 8 to 20 C atoms,        typically linear alkyl. Examples polyoxyethylene lauryl ether,        with 4 or 23 oxyethylene groups; polyoxyethylene cetyl ether        with 2, 10 or 20 oxyethylene groups; polyoxyethylene stearyl        ether, with 2, 10, 20, 21 or 100 oxyethylene groups;        polyoxyethylene (2), (10) oleyl ether, with 2 or 10 oxyethylene        groups. Commercially available examples include, but are not        limited to: ALFONIC, BRIJ, GENAPOL, NEODOL, SURFONIC, TRYCOL.

Nonlimiting examples of ethoxylated materials, such as ethoxylatedsurfactants include compounds having the general formula:R⁸—Z—(CH₂CH₂O)_(s)Bwherein R⁸ is an alkyl group or an alkyl aryl group, selected from thegroup consisting of primary, secondary and branched chain alkylhydrocarbyl groups, primary, secondary and branched chain alkenylhydrocarbyl groups, and/or primary, secondary and branched chain alkyl-and alkenyl-substituted phenolic hydrocarbyl groups having from about 6to about 20 carbon atoms, preferably from about 8 to about 18, morepreferably from about 10 to about 15 carbon atoms; s is an integer fromabout 2 to about 45, preferably from about 2 to about 20, morepreferably from about 2 to about 15; B is a hydrogen, a carboxylategroup, or a sulfate group; and linking group Z is —O—, —C(O)O—,—C(O)N(R)—, or —C(O)N(R)—, and mixtures thereof, in which R, whenpresent, is R⁸ or hydrogen.

The nonionic surfactants herein are characterized by an HLB(hydrophilic-lipophilic balance) of from 5 to 20, preferably from 6 to15.

Nonlimiting examples of preferred ethoxylated surfactant are:

-   -   straight-chain, primary alcohol ethoxylates, with R⁸ being        C₈–C₁₈ alkyl and/or alkenyl group, more preferably C₁₀–C₁₄, and        s being from about 2 to about 8, preferably from about 2 to        about 6;    -   straight-chain, secondary alcohol ethoxylates, with R⁸ being        C₈–C₁₈ alkyl and/or alkenyl, e.g., 3-hexadecyl, 2-octadecyl,        4-eicosanyl, and 5-eicosanyl, and s being from about 2 to about        10;    -   alkyl phenol ethoxylates wherein the alkyl phenols having an        alkyl or alkenyl group containing from 3 to 20 carbon atoms in a        primary, secondary or branched chain configuration, preferably        from 6 to 12 carbon atoms, and s is from about 2 to about 12,        preferably from about 2 to about 8;    -   branched chain alcohol ethoxylates, wherein branched chain        primary and secondary alcohols (or Guerbet alcohols) which are        available, e.g., from the well-known “OXO” process or        modification thereof are ethoxylated.

Especially preferred are alkyl ethoxylate surfactants with each R⁸ beingC₈–C₁₆ straight chain and/or branch chain alkyl and the number ofethyleneoxy groups s being from about 2 to about 6, preferably fromabout 2 to about 4, more preferably with R⁸ being C₈–C₁₅ alkyl and sbeing from about 2.25 to about 3.5. These nonionic surfactants arecharacterized by an HLB of from 6 to about 11, preferably from about 6.5to about 9.5, and more preferably from about 7 to about 9. Nonlimitingexamples of commercially available preferred surfactants are Neodol®91-2.5 (C₉–C₁₀, s=2.7, HLB=8.5), Neodol® 23-3 (C₁₂–C₁₃, s=2.9, HLB=7.9)and Neodol® 25-3 (C₁₂–C₁₅, s=2.8, HLB=7.5.

Further nonlimiting examples include nonionic surfactants selected fromthe group consisting of fatty acid (C₁₂₋₁₈) esters of ethoxylated(EO₅₋₁₀₀) sorbitans. More preferably said surfactant is selected fromthe group consisting of mixtures of laurate esters of sorbitol andsorbitol anhydrides; mixtures of stearate esters of sorbitol andsorbitol anhydrides; and mixtures of oleate esters of sorbitol andsorbitol anhydrides. Even more preferably said surfactant is selectedfrom the group consisting of Polysorbate 20, which is a mixture oflaurate esters of sorbitol and sorbitol anhydrides consistingpredominantly of the monoester, condensed with about 20 moles ofethylene oxide; Polysorbate 60 which is a mixture of stearate esters ofsorbitol and sorbitol anhydride, consisting predominantly of themonoester, condensed with about 20 moles of ethylene oxide; Polysorbate80 which is a mixture of oleate esters of sorbitol and sorbitolanhydrides, consisting predominantly of the monoester, condensed withabout 20 moles of ethylene oxide; and mixtures thereof. Most preferably,said surfactant is Polysorbate 60.

Other examples of ethoxylated surfactant include carboxylated alcoholethoxylate, also known as ether carboxylate, with R⁸ having from about12 to about 16 carbon atoms and s being from about 5 to about 13;ethoxylated quaternary ammonium surfactants, such as PEG-5 cocomoniummethosulfate, PEG-15 cocomonium chloride, PEG-15 oleammonium chlorideand bis(polyethoxyethanol)tallow ammonium chloride.

Other suitable nonionic ethoxylated surfactants are ethoxylated alkylamines derived from the condensation of ethylene oxide with hydrophobicalkyl amines, with R⁸ having from about 8 to about 22 carbon atoms and sbeing from about 3 to about 30.

Also suitable nonionic ethoxylated surfactants for use herein arealkylpolysaccharides which are disclosed in U.S. Pat. No. 4,565,647,Llenado, issued Jan. 21, 1986, having a hydrophobic group containingfrom about 8 to about 30 carbon atoms, preferably from about 10 to about16 carbon atoms and a polysaccharide, e.g., a polyglycoside, hydrophilicgroup containing from about 1.3 to about 10, preferably from about 1.3to about 3, most preferably from about 1.3 to about 2.7 saccharideunits. Any reducing saccharide containing 5 or 6 carbon atoms can beused, e.g., glucose, galactose and galactosyl moieties can besubstituted for the glucosyl moieties. The intersaccharide bonds can be,e.g., between the one position of the additional saccharide units andthe 2-, 3-, 4-, and/or 6-positions on the preceding saccharide units.The preferred alkylpolyglycosides have the formulaR²O(C_(n)H_(2n)O)t(glycosyl)_(x)wherein R² is selected from the group consisting of alkyl, alkylphenyl,hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which thealkyl groups contain from 10 to 18, preferably from 12 to 14, carbonatoms; n is 2 or 3, preferably from about 1.3 to about 3, mostpreferably from about 1.3 to about 2.7. The glycosyl is preferablyderived from glucose.

In one embodiment, the nonionic surfactants comprise polyhydroxy fattyacid amide surfactants of the formula:R²—C(O)—N(R¹)—Z,wherein R¹ is H, or R¹ is C₁₋₄ hydrocarbyl, 2-hydroxy ethyl, 2-hydroxypropyl or a mixture thereof, R² is C₅₋₃₁ hydrocarbyl, and Z is apolyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3hydroxyls directly connected to the chain, or an alkoxylated derivativethereof. Preferably, R¹ is methyl, R² is a straight C₁₁₋₁₅ alkyl orC₁₆₋₁₈ alkyl or alkenyl chain such as coconut alkyl or mixtures thereof,and Z is derived from a reducing sugar such as glucose, fructose,maltose, lactose, in a reductive amination reaction.

In one embodiment, the anionic surfactants include alkyl alkoxylatedsulfate surfactants hereof are water soluble salts or acids of theformula RO(A)_(m)SO3M wherein R is an unsubstituted C₁₀–C₂₄ alkyl orhydroxyalkyl group having a C₁₀–C₂₄ alkyl component, preferably aC₁₂–C₂₀ alkyl or hydroxyalkyl, more preferably C₁₂–C₁₈ alkyl orhydroxyalkyl, A is an ethoxy or propoxy unit, m is greater than zero,typically between about 0.5 and about 6, more preferably between about0.5 and about 3, and M is H or a cation which can be, for example, ametal cation (e.g., sodium, potassium, lithium, calcium, magnesium,etc.), ammonium or substituted-ammonium cation. Alkyl ethoxylatedsulfates as well as alkyl propoxylated sulfates are contemplated herein.

These and other surfactants suitable for use in combination with thelipophilic fluid as adjuncts are well known in the art, being describedin more detail in Kirk Othmer's Encyclopedia of Chemical Technology, 3rdEd., Vol. 22, pp. 360–379, “Surfactants and Detersive Systems”,incorporated by reference herein. Further suitable nonionic detergentsurfactants are generally disclosed in U.S. Pat. No. 3,929,678, Laughlinet al., issued Dec. 30, 1975, at column 13, line 14 through column 16,line 6, incorporated herein by reference.

The non-silicone additive, when present in the fabric article treatingcompositions of the present invention, preferably comprises from about0.01% to about 10%, more preferably from about 0.02% to about 5%, evenmore preferably from about 0.05% to about 2% by weight of the fabricarticle treating composition.

The non-silicone additive, when present in the consumable detergentcompositions of the present invention, preferably comprises from about1% to about 90%, more preferably from about 2% to about 75%, even morepreferably from about 5% to about 60% by weight of the consumabledetergent composition.

In one embodiment, the surfactant component comprises a non-siliconeadditive.

In another embodiment, the surfactant component does not comprise anon-silicone additive.

Polar Solvent

Compositions according to the present invention may further comprise apolar solvent. Non-limiting examples of polar solvents include: water,alcohols, glycols, polyglycols, ethers, carbonates, dibasic esters,ketones, other oxygenated solvents, and mixutures thereof. Furtherexamples of alcohols include: C1–C126 alcohols, such as propanol,ethanol, isopropyl alcohol, etc. . . . , benzyl alcohol, and diols suchas 1,2-hexanediol. The Dowanol series by Dow Chemical are examples ofglycols and polyglycols useful in the present invention, such as DowanolTPM, TPnP, DPnB, DPnP, TPnB, PPh, DPM, DPMA, DB, and others. Furtherexamples include propylene glycol, butylene glycol, polybutylene glycoland more hydrophobic glycols. Examples of carbonate solvents areethylene, propylene and butylene carbonantes such as those availableunder the Jeffsol® tradename. Polar solvents for the present inventioncan be further identified through their dispersive (δ_(D)), polar(δ_(P)) and hydrogen bonding (δ_(H)) Hansen solubility parameters.Preferred polar solvents or polar solvent mixtures have fractional polar(f_(P)) and fractional hydrogen bonding (f_(H)) values of f_(P)>0.02 andf_(H)>0.10, where f_(P)=δ_(P)/(δ_(D)+δ_(P)+δ_(H)) andf_(H)=δ_(H)/(δ_(D)+δ_(P)+δ_(H)), more preferably f_(p)>0.02 andf_(H)>0.20, and most preferably f_(P)>0.07 and f_(H)>0.30.

In the detergent composition of the present invention, the levels ofpolar solvent can be from about 0 to about 70%, preferably 1 to 50%,even more preferably 1 to 30% by weight of the detergent composition.

Water, when present in the wash fluid fabric article treatingcompositions of the present invention, the wash fluid composition maycomprise from about 0.001% to about 10%, more preferably from about0.005% to about 5%, even more preferably from about 0.01% to about 1% byweight of the wash fluid fabric article treating composition.

Water, when present in the detergent compositions of the presentinvention, preferably comprises from about 1% to about 90%, morepreferably from about 2% to about 75%, even more preferably from about5% to about 40% by weight of the consumable detergent composition.

Processing Aids

Optionally, the compositions of the present invention may furthercomprise processing aids. Processing aids facilitate the formation ofthe fabric article treating compositions of the present invention, bymaintaining the fluidity and/or homogeneity of the consumable detergentcomposition, and/or aiding in the dilution process. Processing aidssuitable for the present invention are solvents, preferably solventsother than those described above, hydrotropes, and/or surfactants,preferably surfactants other than those described above with respect tothe surfactant component. Particularly preferred processing aids areprotic solvents such as aliphatic alcohols, diols, triols, etc. andnonionic surfactants such as ethoxylated fatty alcohols.

Processing aids, when present in the fabric article treatingcompositions of the present invention, preferably comprise from about0.02% to about 10%, more preferably from about 0.05% to about 10%, evenmore preferably from about 0.1% to about 10% by weight of the fabricarticle treating composition.

Processing aids, when present in the consumable detergent compositionsof the present invention, preferably comprise from about 1% to about75%, more preferably from about 5% to about 50% by weight of theconsumable detergent composition.

Cleaning Adjuncts

The compositions of the present invention may optionally furthercomprise one or more cleaning adjuncts. The optional cleaning adjunctscan vary widely and can be used at widely ranging levels. For example,detersive enzymes such as proteases, amylases, cellulases, lipases andthe like as well as bleach catalysts including the macrocyclic typeshaving manganese or similar transition metals all useful in laundry andcleaning products can be used herein at very low, or less commonly,higher levels. Cleaning adjuncts that are catalytic, for exampleenzymes, can be used in “forward” or “reverse” modes, a discoveryindependently useful from the fabric treating methods of the presentinvention. For example, a lipolase or other hydrolase may be used,optionally in the presence of alcohols as cleaning adjuncts, to convertfatty acids to esters, thereby increasing their solubility in thelipophilic fluid. This is a “reverse” operation, in contrast with thenormal use of this hydrolase in water to convert a less water-solublefatty ester to a more water-soluble material. In any event, any cleaningadjunct must be suitable for use in combination with a lipophilic fluidin accordance with the present invention.

Some suitable cleaning adjuncts include, but are not limited to,builders, surfactants, other than those described above with respect tothe surfactant component, enzymes, bleach activators, bleach catalysts,bleach boosters, bleaches, alkalinity sources, antibacterial agents,colorants, perfumes, pro-perfumes, finishing aids, lime soapdispersants, odor control agents, odor neutralizers, polymeric dyetransfer inhibiting agents, crystal growth inhibitors, photobleaches,heavy metal ion sequestrants, anti-tarnishing agents, anti-microbialagents, anti-oxidants, anti-redeposition agents, soil release polymers,electrolytes, pH modifiers, thickeners, abrasives, divalent or trivalentions, metal ion salts, enzyme stabilizers, corrosion inhibitors,polyamines and/or their alkoxylates, suds stabilizing polymers,solvents, process aids, fabric softening agents, optical brighteners,hydrotropes, suds or foam suppressors, suds or foam boosters andmixtures thereof.

Suitable odor control agents, which may optionally be used as finishingagents, include agents include, cyclodextrins, odor neutralizers, odorblockers and mixtures thereof. Suitable odor neutralizers includealdehydes, flavanoids, metallic salts, water-soluble polymers, zeolites,activated carbon and mixtures thereof.

Perfumes and perfumery ingredients useful in the compositions of thepresent invention comprise a wide variety of natural and syntheticchemical ingredients, including, but not limited to, aldehydes, ketones,esters, and the like. Also included are various natural extracts andessences which can comprise complex mixtures of ingredients, such asorange oil, lemon oil, rose extract, lavender, musk, patchouli, balsamicessence, sandalwood oil, pine oil, cedar, and the like. Finishedperfumes may comprise extremely complex mixtures of such ingredients.Pro-perfumes are also useful in the present invention. Such materialsare those precursors or mixtures thereof capable of chemically reacting,e.g., by hydrolysis, to release a perfume, and are described in patentsand/or published patent applications to Procter and Gamble, Firmenich,Givaudan and others.

Bleaches, especially oxygen bleaches, are another type of cleaningadjunct suitable for use in the compositions of the present invention.This is especially the case for the activated and catalyzed forms withsuch bleach activators as nonanoyloxybenzenesulfonate and/or any of itslinear or branched higher or lower homologs, and/ortetraacetylethylenediamine and/or any of its derivatives or derivativesof phthaloylimidoperoxycaproic acid (PAP) or other imido- oramido-substituted bleach activators including the lactam types, or moregenerally any mixture of hydrophilic and/or hydrophobic bleachactivators (especially acyl derivatives including those of the C₆–C₁₆substituted oxybenzenesulfonates).

Also suitable are organic or inorganic peracids both including PAP andother than PAP. Suitable organic or inorganic peracids for use hereininclude, but are not limited to: percarboxylic acids and salts;percarbonic acids and salts; perimidic acids and salts;peroxymonosulfuric acids and salts; persulphates such as monopersulfate;peroxyacids such as diperoxydodecandioic acid (DPDA); magnesiumperoxyphthalic acid; perlauric acid; perbenzoic and alkylperbenzoicacids; and mixtures thereof.

One class of suitable organic peroxycarboxylic acids has the generalformula:

wherein R is an alkylene or substituted alkylene group containing from 1to about 22 carbon atoms or a phenylene or substituted phenylene group,and Y is hydrogen, halogen, alkyl, aryl, —C(O)OH or —C(O)OOH.

Particularly preferred peracid compounds are those having the formula:

wherein R is C₁₋₄ alkyl and n is an integer of from 1 to 5. Aparticularly preferred peracid has the formula where R is CH₂ and n is 5i.e., phthaloylamino peroxy caproic acid (PAP) as described in U.S. Pat.Nos. 5,487,818, 5,310,934, 5,246,620, 5,279,757 and 5,132,431. PAP isavailable from Ausimont SpA under the tradename Euroco®.

Other cleaning adjuncts suitable for use in the compositions of thepresent invention include, but are not limited to, builders includingthe insoluble types such as zeolites including zeolites A, P and theso-called maximum aluminum P as well as the soluble types such as thephosphates and polyphosphates, any of the hydrous, water-soluble orwater-insoluble silicates, 2,2′-oxydisuccinates, tartrate succinates,glycolates, NTA and many other ethercarboxylates or citrates; chelantsincluding EDTA, S,S′-EDDS, DTPA and phosphonates; water-solublepolymers, copolymers and terpolymers; soil release polymers; opticalbrighteners; processing aids such as crisping agents and/fillers;anti-redeposition agents; hydrotropes, such as sodium, or calcium cumenesulfonate, potassium napthalenesulfonate, or the like, humectant; otherperfumes or pro-perfumes; dyes; photobleaches; thickeners; simple salts;alkalis such as those based on sodium or potassium including thehydroxides, carbonates, bicarbonates and sulfates and the like; andcombinations of one or more of these cleaning adjuncts.

Suitable finishing aids include, but are not limited to, finishingpolymers; such as synthetic or natural polyacrylates or starchcarboxymethyl cellulose or hydroxypropyl methyl cellulose, odor controlagents, odor neutralizers, perfumes, properfumes, anti-static agents,fabric softeners, insect and/or moth repelling agents and mixturesthereof.

The finishing polymers can be natural, or synthetic, and can act byforming a film, and/or by providing adhesive properties to adhere thefinishing polymers to the fabrics. By way of example, the compositionsof the present invention can optionally use film-forming and/or adhesivepolymer to impart shape retention to fabric, particularly clothing. By“adhesive” it is meant that when applied as a solution or a dispersionto a fiber surface and dried, the polymer can attach to the surface. Thepolymer can form a film on the surface, or when residing between twofibers and in contact with the two fibers, it can bond the two fiberstogether.

Nonlimiting examples of finishing polymers that are commerciallyavailable are: polyvinylpyrrolidone/dimethylaminoethyl methacrylatecopolymer, such as Copolymer 958®, molecular weight of about 100,000 andCopolymer 937®, molecular weight of about 1,000,000, available from GAFChemicals Corporation; adipic acid/dimethylaminohydroxypropyldiethylenetriamine copolymer, such as Cartaretin F-4® and F-23,available from Sandoz Chemicals Corporation; methacryloyl ethylbetaine/methacrylates copolymer, such as Diaformer Z-SM®, available fromMitsubishi Chemicals Corporation; polyvinyl alcohol copolymer resin,such as Vinex 2019®, available from Air Products and Chemicals orMoweol®, available from Clariant; adipic acid/epoxypropyldiethylenetriamine copolymer, such as Delsette 101φ, available fromHercules Incorporated; polyamine resins, such as Cypro 515®, availablefrom Cytec Industries; polyquaternary amine resins, such as Kymene557H®, available from Hercules Incorporated; andpolyvinylpyrrolidone/acrylic acid, such as Sokalan EG 310®, availablefrom BASF.

The cleaning adjunct may also be an antistatic agent. Any suitablewell-known antistatic agents used in conventional laundering and drycleaning are suitable for use in the compositions and methods of thepresent invention. Especially suitable as antistatic agents are thesubset of fabric softeners which are known to provide antistaticbenefits. For example those fabric softeners that have a fatty acylgroup which has an iodine value of above 20, such asN,N-di(tallowoyl-oxy-ethyl)-N,N-dimethyl ammonium methylsulfate.However, it is to be understood that the term antistatic agent is not tobe limited to just this subset of fabric softeners and includes allantistatic agents.

Preferred insect and moth repellent cleaning adjuncts useful in thecompositions of the present invention are perfume ingredients, such ascitronellol, citronellal, citral, linalool, cedar extract, geranium oil,sandalwood oil, 2-(diethylphenoxy)ethanol, 1-dodecene, etc. Otherexamples of insect and/or moth repellents useful in the compositions ofthe present invention are disclosed in U.S. Pat. Nos. 4,449,987;4,693,890; 4,696,676; 4,933,371; 5,030,660; 5,196,200; and in “SemioActivity of Flavor and Fragrance Molecules on Various Insect Species”,B. D. Mookherjee et al., published in Bioactive Volatile Compounds fromPlants, ACS Symposium Series 525, R. Teranishi, R. G. Buttery, and H.Sugisawa, 1993, pp. 35–48, all of said patents and publications beingincorporated herein by reference.

Examples of Fabric Article Treating Compositions

The following are non-limiting examples of fabric article treatingcompositions in accordance with the present invention.

TABLE 1 A B C D E F Lipophilic To 100% To 100% To 100% To 100% To 100%To 100% Fluid Surfactant 0.3% 0.2% 0.2% 0.1%  10% 5% Component(s)Non-silicone 0.4% 0.15%  0.2% 0.2%   5% 1% Additive(s) Polar — —   5%0.325%  0.6% 0.28%   Solvent(s)Examples of Consumable Detergent Compositions

The following are nonlimiting examples of consumable detergentcompositions in accordance with the present invention:

TABLE 2 A B C D E F Surfactant 33% 82% 50% 16% 35% 15% Component(s)Non-silicone 67%  5% 50% 32% 32% 33% Additive(s) Polar — Balance —Balance Balance Balance Solvent(s)

Treated Fabric Article

A fabric article that has been treated in accordance a method of thepresent invention is also within the scope of the present invention.Preferably such a treated fabric article comprises an analyticallydetectable amount of at least one compound (e.g., an organosilicone)having a surface energy modifying effect but no antistatic effect; or ananalytically detectable amount of at least one compound having a surfaceenergy modifying and/or feel-modifying and/or comfort-modifying and/oraesthetic effect and at least one antistatic agent other than said atleast one compound.

1. A fabric article treating composition comprising: a) from about 70%to about 99.99% by weight of the fabric article treating composition ofdecamethylcyclopentasiloxane; b) from about 0.01% to about 10% by weightof the fabric article treating composition of a siloxane-basedsurfactant; c) from about 0.01% to about 10% by weight of the fabricarticle treating composition of a nonionic surfactant which is differentfrom the siloxane-based surfactant; d) from about 0.001% to about 10% byweight of the fabric article treating composition of a polar solventcomprising 1,2-hexanediol; and e) optionally, from about 0.01% to about10% by weight of the fabric article treating composition of othercleaning adjuncts.
 2. The fabric article treating composition accordingto claim 1 wherein the nonionic surfactant comprises an ethoxylatedsurfactant having the formula:R⁸—Z—(CH₂CH₂O)_(s)B wherein R⁸ is an alkyl group or an alkyl aryl group,selected from the group consisting of primary, secondary and branchedchain alkyl hydrocarbyl groups, primary, secondary and branched chainalkenyl hydrocarbyl groups, and/or primary, secondary and branched chainalkyl- and alkenyl-substituted phenolic hydrocarbyl groups having fromabout 6 to about 20 carbon atoms; s is an integer from about 2 to about45; B is a hydrogen, a carboxylate group, or a sulfate group; andlinking group Z is —O—, —C(O)O, —C(O)N(R)—, or —C(O)N(R)—, and mixturesthereof, in which R, when present, is R⁸ or hydrogen.
 3. The fabricarticle treating composition according to claim 2 wherein the nonionicsurfactant comprises a secondary alcohol ethoxylate, with R⁸ beingC₈–C₁₈ alkyl and/or alkenyl group, and s being from about 2 to about 8.4. The fabric article treating composition according to claim 2 whereinthe nonionic surfactant comprises an alkyl ethoxylate, with R⁸ beingC₈–C₁₆ straight or branched chain alkyl and/or alkenyl group, and sbeing from about 2 to about
 6. 5. The fabric article treatingcomposition according to claim 2 wherein the nonionic surfactantcomprises an alkyl ethoxylate, with R⁸ being C₈–C₁₅ alkyl group, and sbeing from about 2.25 to about 3.5.
 6. The fabric article treatingcomposition according to claim 2 wherein the nonionic surfactant has anHLB of from about 6 to about
 11. 7. The fabric article treatingcomposition according to claim 1 wherein said surfactant componentcomprises a siloxane-based surfactant comprising a polyether siloxanehaving the formula:M_(a)D_(b)D′_(c)D″_(d)M′_(2-a) wherein a is 0–2; b is 0–1000; c is 0–50;d is 0–50, provided that a+c+d is at least 1; M is R¹ _(3-e)X_(e)SiO_(½)wherein R¹ is independently H, or a monovalent hydrocarbon group, X ishydroxyl group, and e is 0 or 1; M′ is R² ₃SiO_(½) wherein R² isindependently H, a monovalent hydrocarbon group, or(CH₂)_(f)—(C6H4)_(g)O—(C₂H₄O)_(h)—(C₃H₆O)_(i)—(C_(k)H_(2K)O)_(j)—R₃,provided that at least one R² is(CH₂)_(f)—(C6H4)_(g)O—(C₂H₄O)_(h)—(C₃H₆O)_(i)—(C_(k)H_(2K)O)_(j)—R³,wherein R³ is independently H, a monovalent hydrocarbon group or analkoxy group, f is 1–10, g is 0 or 1, h is 1–50, i is 0–50, j is 0–50, kis 4–8; D is R⁴ ₂SiO_(2/2) wherein R⁴ is independently H or a monovalenthydrocarbon group; D′ is R⁵ ₂SiO_(2/2) wherein R⁵ is independently R²provided that at least one R⁵ is(CH₂)_(f)—(C6H4)_(g)O—(C₂H₄O)_(h)—(C₃H₆O)_(i)—(C_(k)H_(2K)O)_(j)—R³,wherein R³ is independently H, a monovalent hydrocarbon group or analkoxy group, f is 1–10, g is 0 or 1, h is 1–50, i is 0–50, j is 0–50, kis 4–8; and D″ is R⁶ ₂SiO_(2/2) wherein R⁶ is independently H, amonovalent hydrocarbon group or(CH₂)_(l)(C₆H₄)_(m)(A)_(n)—[(L)_(o)—(A′)_(p)—]_(q)—(L′)_(r)Z(G)_(s),wherein l is 1–10; m is 0 or 1; n is 0–5; o is 0–3; p is 0 or 1; q is0–10; r is 0–3; s is 0–3; C₆H₄ is unsubstituted or substituted with aC₁₋₁₀ alkyl or alkenyl; A and A′ are each independently a linking moietyrepresenting an ester, a keto, an ether, a thio, an amido, an amino, aC₁₋₄ fluoroalkyl, a C₁₋₄ fluoroalkenyl, a branched or straight chainedpolyalkylene oxide, a phosphate, a sulfonyl, a sulfate, an ammonium, andmixtures thereof; L and L′ are each independently a C₁₋₃₀ straightchained or branched alkyl or alkenyl or an aryl which is unsubstitutedor substituted; Z is a hydrogen, carboxylic acid, a hydroxy, aphosphato, a phosphate ester, a sulfonyl, a sulfonate, a sulfate, abranched or straight-chained polyalkylene oxide, a nitryl, a glyceryl,an aryl unsubstituted or substituted with a C₁₋₃₀ alkyl or alkenyl, acarbohydrate unsubstituted or substituted with a C₁₋₁₀ alkyl or alkenylor an ammonium; G is an anion or cation such as H⁺, Na⁺, Li⁺, K⁺, NH₄ ⁺,Ca⁺², Mg⁺², Cl⁻, Br⁻, I⁻, mesylate or tosylate.
 8. The fabric articletreating composition according to claim 1 further comprising from about1% to about 60% by weight of the composition of a non-silicone additiveselected from the group consisting of anionic, cationic, zwitterionicsurfactants and mixtures thereof.
 9. The fabric article treatingcomposition of claim 1, wherein the polar solvent further compriseswater.
 10. The fabric article treating composition according to claim 1wherein said composition further comprises a cleaning adjunct selectedfrom the group consisting of: builders, additional surfactants,emulsifying agents, enzymes, bleach activators, bleach catalysts, bleachboosters, bleaches, alkalinity sources, antibacterial agent, colorants,perfume, lime soap dispersants, odor control agents, odor neutralizers,polymeric dye transfer inhibiting agents, crystal growth inhibitors,photobleaches, heavy metal ion sequestrants, anti-tarnishing agents,anti-microbial agents, anti-oxidants, anti-redeposition agents, soilrelease polymers, electrolytes, pH modifiers, thickeners, abrasives,divalent ions, metal ion salts, enzyme stabilizers, corrosioninhibitors, diamines, suds stabilizing polymers, solvents, process aids,fabric softening agents or actives, sizing agents, optical brighteners,hydrotropes and mixtures thereof.
 11. A method for laundering fabricarticles in need of treatment comprising the steps of: a) obtaining afabric article treating composition and according to claim 1; b)contacting the fabric articles with the fabric article treatingcomposition from step a), such that the fabric articles are treated.